scholarly journals Molecular Structure of Nickel Octamethylporphyrin—Rare Experimental Evidence of a Ruffling Effect in Gas Phase

2021 ◽  
Vol 23 (1) ◽  
pp. 320
Author(s):  
Alexander E. Pogonin ◽  
Arseniy A. Otlyotov ◽  
Yury Minenkov ◽  
Alexander S. Semeikin ◽  
Yuriy A. Zhabanov ◽  
...  
Keyword(s):  
Gas Phase ◽  
Density Functional ◽  
Central Atom ◽  
Critical Distance ◽  
Problem Solution ◽  
Functional Theory ◽  
Inverse Problem Solution ◽  
Metal Porphyrins ◽  
First Time ◽  
Gas Phase Electron Diffraction

The structure of a free nickel (II) octamethylporphyrin (NiOMP) molecule was determined for the first time through a combined gas-phase electron diffraction (GED) and mass spectrometry (MS) experiment, as well as through quantum chemical (QC) calculations. Density functional theory (DFT) calculations do not provide an unambiguous answer about the planarity or non-planar distortion of the NiOMP skeleton. The GED refinement in such cases is non-trivial. Several approaches to the inverse problem solution were used. The obtained results allow us to argue that the ruffling effect is manifested in the NiOMP molecule. The minimal critical distance between the central atom of the metal and nitrogen atoms of the coordination cavity that provokes ruffling distortion in metal porphyrins is about 1.96 Å.

Molecular Structure of Ru(η-C5Me5)(η-C5F5) by Gas-Phase Electron Diffraction and Density Functional Theory

2002 ◽  
Vol 21 (22) ◽  
pp. 4840-4846 ◽  
Author(s):  
Blair F. Johnston ◽  
David W. H. Rankin ◽  
Heather E. Robertson ◽  
Russell P. Hughes ◽  
Jeffrey R. Lomprey
Keyword(s):  
Molecular Structure ◽  
Density Functional Theory ◽  
Electron Diffraction ◽  
Gas Phase ◽  
Density Functional ◽  
Functional Theory ◽  
Gas Phase Electron Diffraction

Intrinsic Stacking Interactions of Natural and Artificial Nucleobases

2019 ◽  
Author(s):  
Drew P. Harding ◽  
Laura J. Kingsley ◽  
Glen Spraggon ◽  
Steven Wheeler
Keyword(s):  
Gas Phase ◽  
Electrostatic Interactions ◽  
Density Functional ◽  
Molecular Descriptors ◽  
Stacking Interactions ◽  
Interaction Energies ◽  
Functional Theory ◽  
Binding Partner ◽  
Heavy Atoms ◽  
Wide Range

The intrinsic (gas-phase) stacking energies of natural and artificial nucleobases were explored using density functional theory (DFT) and correlated ab initio methods. Ranking the stacking strength of natural nucleobase dimers revealed a preference in binding partner similar to that seen from experiments, namely G > C > A > T > U. Decomposition of these interaction energies using symmetry-adapted perturbation theory (SAPT) showed that these dispersion dominated interactions are modulated by electrostatics. Artificial nucleobases showed a similar stacking preference for natural nucleobases and were also modulated by electrostatic interactions. A robust predictive multivariate model was developed that quantitively predicts the maximum stacking interaction between natural and a wide range of artificial nucleobases using molecular descriptors based on computed electrostatic potentials (ESPs) and the number of heavy atoms. This model should find utility in designing artificial nucleobase analogs that exhibit stacking interactions comparable to those of natural nucleobases. Further analysis of the descriptors in this model unveil the origin of superior stacking abilities of certain nucleobases, including cytosine and guanine.

scholarly journals Single-crystalline epitaxial TiO film: A metal and superconductor, similar to Ti metal

2021 ◽  
Vol 7 (2) ◽  
pp. eabd4248
Author(s):  
Fengmiao Li ◽  
Yuting Zou ◽  
Myung-Geun Han ◽  
Kateryna Foyevtsova ◽  
Hyungki Shin ◽  
...  
Keyword(s):  
Transition Metal ◽  
Density Functional ◽  
Tight Binding ◽  
Crystal Form ◽  
Titanium Monoxide ◽  
Binding Model ◽  
Functional Theory ◽  
Single Crystalline ◽  
First Time ◽  
Lattice Matched

Titanium monoxide (TiO), an important member of the rock salt 3d transition-metal monoxides, has not been studied in the stoichiometric single-crystal form. It has been challenging to prepare stoichiometric TiO due to the highly reactive Ti2+. We adapt a closely lattice-matched MgO(001) substrate and report the successful growth of single-crystalline TiO(001) film using molecular beam epitaxy. This enables a first-time study of stoichiometric TiO thin films, showing that TiO is metal but in proximity to Mott insulating state. We observe a transition to the superconducting phase below 0.5 K close to that of Ti metal. Density functional theory (DFT) and a DFT-based tight-binding model demonstrate the extreme importance of direct Ti–Ti bonding in TiO, suggesting that similar superconductivity exists in TiO and Ti metal. Our work introduces the new concept that TiO behaves more similar to its metal counterpart, distinguishing it from other 3d transition-metal monoxides.

Graph theory-based reaction pathway searches and DFT calculations for the mechanism studies of free radical-initiated peptide sequencing mass spectrometry (FRIPS MS): a model gas-phase reaction of GGR tri-peptide

2020 ◽  
Vol 22 (9) ◽  
pp. 5057-5069 ◽  
Author(s):  
Jae-ung Lee ◽  
Yeonjoon Kim ◽  
Woo Youn Kim ◽  
Han Bin Oh
Keyword(s):  
Graph Theory ◽  
Dft Calculations ◽  
Gas Phase ◽  
Density Functional ◽  
Reaction Pathway ◽  
Peptide Sequencing ◽  
Phase Reaction ◽  
Functional Theory ◽  
Fragmentation Mechanisms ◽  
Gas Phase Fragmentation

A new approach for elucidating gas-phase fragmentation mechanisms is proposed: graph theory-based reaction pathway searches (ACE-Reaction program) and density functional theory (DFT) calculations.

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